Edible oil blends



V F f United States ate: 0 ice 85,854 g Patented June .1, 1965 with thenatural salad oils or with other oils which have 3 5 been subjected toan initial Winterizing treatment. Nor EEELE 9H. ELENDS Louis H. Going,lowland, Ulric, assignor to The Procter & Gamble Company, Cincinnati,@hio, a corporation of Ghio No Drawing. Filed duly 6, 1962, Ser. No.208,109

9' Claims. (Cl. 99-163) This invention relates to improved edible oilblends. More particularly, it relates to mixtures of triglyceride oilswhich can be stored at relatively low temperatures for extended periodsor" time without clouding, and which are capable of being used as saladoils. 7

Many liquid triglyceride oils normally deposit stearin or otherwisebecome cloudy at low temperatures whereby their visual appearance andphysical characteristics are impaired. It is well known that suchclouded oils are considered objectionable by the housewife and otherconsumers. Unless these oils remain substantially clear at thetemperatures ordinarily encountered, they will not be acceptable assalad oils for table use and the like. In this connection it must beremembered that the temperatures which have to be resisted are not onlyhome refrigeration temperatures which generally run as low as 40 to 50F. but also freezing temperatures of 32 F. and lower which may beencountered for periods of time during storage and shipment in coldclimates.

The resistance of an edible triglyceride oil to clouding at lowtemperatures is conveniently shown by means of a well-known standardizedchill test (Qiiicial Method Cc 1l-53 of the American Oil ChemistsSociety). If the oilis tree from clouding at 32 F. for at least 5 /2hours when subjected to this chill test procedure, itis generallyconsidered to be a suitable salad oil for use in mayonnaise and thelike.

Certain oils, such as corn oil, soybean oil and olive oil, are naturalsalad oils since they contain relatively small proportions of the moresaturated glycerides which tend to separate out when the oil is storedat low temperatures. But even these so-called natural salad oilsfrequently are subjected .to treatment of one sort or another to furtherimprove their resistance to clouding at low temperatures,

Other oils, such as cottonseed oil or soybean oil which has beenpartially hydrogenated to improve its oxidative stability, exhibit poorresistance to cold temperatures and have a strong tendency to depositstearin and other high melting solids. Although such oils generally canbe used as cooking oils, they are not suitable for salad oil purposesunless they are treated in some manner whereby the said stearin or othercrystal-tending constituents are either removed or inhibited.

One of the most common methods used by oil technologists for improvingthe resistance of triglyceride oils to clouding at low temperaturesconsists of subjecting the oil to a so-called Winterizing treatmentwhereby the stearin and other high melting constituents are removed byfractional crystallization. Another method consists of inhibiting theclouding of salad oils by adding a small amount of a crystallizationinhibitor to the oil. I

Neibher of the aforesaid methods is wholly suitable to the oil trade,however, since the usual Winterizing.

treatment involves a time-consuming and costly procedure, and the knowncrystallization inhibitors heretofore have been significantly eiiectiveonly when used in connection has the substitution of certain'naturalsalad oils such as corn oil or soybean oil for winterized cottonseed oilproved entirely suitable, since the former oils exhibit a greatertendency to revert in flavor over periods of time. A means for improvingthe resistance to clouding at low temperatures of poorly resistant oils,such as cottonseed oil and partially hydrogenated soybean oil, withoutsubjecting them to the usual degree of Winterizing treatment I would beextremely useful- Accordingly, it is an object of this invention toprovide novel oil blends whereby an oil blend component which normallyhas poor resistance to clouding at low temperablends having improvedflavor characteristics and stability.

It has now been discovered that the resistance to clouding at lowtemperature of a summer oil having relatively poor resistance toclouding can be significantly improved and upgraded by blending it incertain proportions with a winter oil having good resistance to cloudingand adding thereto a small amount of a conventional crystallizationinhibitor;

As used herein, the term summer oil is intended to define a triglycerideoil which is substantially liquid at 60 F. but which has a chill test ofless than 5 /2 hours according to the procedure described hereinbeforeand has poor resistance to clouding in'the presence of a crystallizationinhibitor.

As used herein, the term Winter oil is intended to define a liquidtriglyceride oil which has good resistance to clouding and has a chilltest of at least 5 /2 hours according to the procedure describedhereinbefore.

As used herein, the term crystallization inhibitor is intended to definea high molecular Weight substance having both lipophilic and lipophobicgroups which is capable of substantially improving the chill test of awinter oil by retardin the formation of clouding Without adverselyaiiecting its interfacial tension with respect to its normal salad oilusage.

It has been found that substantial and unexpected im-' provements in thechill test of blends of summer and,

should equal about 0.5 to about 1.0. More specifically, 1 should equalabout 0.5 to about 1.0 when I is the transmitted intensity of the winteroil component and I is the transmitted intensity of the uninhibitedblend of summer and winter oils when held at a temperature of 335 F. fora period of minutes and photoelectrically measured with monochromaticlight having a wave length I of 600 m a The improvements obtained withthe novel oil blends of this invention are completely anomalous. Thus,it is contrary to the teachings of oil technologists to blend a portionof a natural salad oil or other winter oil into a summer oil in anattempt to improve the resistance of the latter oil to clouding at lowtemperatures. It is well- 7 known that the practical result of such anattempt will be a substantial downgrading of the .winter oil rather thana material upgrading of the summer oil. This natural result which isobtained in practice is easily explainable on the basis of the fact thatthe stearin and other high melting solids of the summer oil are stillpresent in the oil blend and, therefore, will cause clouding when theblend is subjected to low temperatures. The degree of intersolubilitybetween such oils is usually so poor that there isnegligible-improvement in the resistance to clouding of the summer oilconstituent of the blend.

Moreover, it is also known that the conventional crystallizationinhibitors are relatively ineffective for improving the resistance toclouding at low temperature of summer oils. The usual inhibitormaterials have been found to have little or no eifeot upon the highmelting solids found in a summer oil such as cottonseed oil .orpartially hydrogenated soy-bean oil.

Examples of winter oils used in the compositions of this invention arethe natural salad oils such assoybean oil, corn oil, olive oil,safflower oil, sunflower oil, sesame oil, and the winterized oils suchas winterized cottonseed oil or winterized partially hydrogenatedsoybean oil.

The most common example of a summer oil which can be used in thepractice of this invention is cottonseed oil. The abundant supply ofcottonseed oil has led to its'wide-spread use in salad dressings.However, it has been necessary heretofore to subject cottonseed oil to aWinterizing treatment to remove its higher melting constituents in orderto make it suitable as a salad oil. 7

Another usable summer oil is peanut oil. However, since peanut oil tendsto deposit very difiiculty filterable crystals, it has not been commonpractice heretofore to winterize it for salad oil purposes. Instead, ithas been used primarily as a cooking oil.

Other examples of summer oils used in this invention are the naturalvegetable oils which have been partially hydrogenated in order toimprove their oxidative stability.

Examples of crystallization inhibitors which can be used in the practiceof this invention are lecithin and other vegetable phosphatides; certainesters of polyhydric alcohols and other hydroxycompounds with long chain.fatty acids such as those described in US. Patent 2,266,- 591, grantedDecember 16, 1941, to Eckeyand Lutton; oxygenated and thermally modifiedhardened vegetable oils such as the oxystearin described hereinafter;oxidized and polymerized oils such'as described in U.S.- Patent2,097,720, granted November 2, 1937, to Clayton et al.; certain estersof disaccharides such as sucrose, maltose and lactose with fatty acids,said disaccharide being esterified with an average of from about 15% to85%, based on the total fatty acid inthe ester, of saturated fatty acidshaving from 14 to 22 carbon atoms, the balance of the fatty acidsbeingseleoted from the group consisting of fatty acids having from 2tolZ carbon atoms and unsaturated fatty acids having from 14 to 22carbon atoms, said ester having an average of not more than 5unesterified hydroxyl groups per molecule; certain esters of dextrinwith fatty acids, said dextrin being esterified with.

an average of from about /2 to 2 acyl groups of saturated fattyaoids'having from 14 to 22 carbon atoms, the bal-, ance of the fattyacids of said ester being selected from the group consisting of fattyacids having from 2 to 12 carbon atoms and unsaturated fatty acidshaving from 14 to 22 carbon atoms, said ester having an average of notmore than 1 /2. unesterified hydroxyl groups per glucose unit; certainesters of monosaccharidic material having an oxide ring structure andselectedfrom the group consisting of aldohexose, aldohexuronolactone,aldohexuronic acid, aldohexonolactone, and methyl aldohexoside withfatty acids, said material being at least 25% esterified, based on thetotal hydroxyl availability, with at least 15%, based on the total fattyacid in the ester, of saturated long chain fatty acid having from about12 to about 24 carbon atoms, the balance of the fatty acid beingselected from the group consisting of short chain fatty acids havingfrom 2 to about 6 carbon atoms and unsaturated long chain fatty acidshaving from about 12 to about 24 carbon atoms in such a manner that themolar proportion of said short chain fatty acids does not substantiallyexceed the total molar proportion of said saturated and unsaturatedlongchain fatty acids.

Although specific summer and winter oils and specific crystallizationinhibitors are mentioned herein, the invention is not'lirnited to theseparticular materials.

It will be understood that certain combinations of summer and winteroils are particularly desirable for.

purposes of this invention, although the invention is not limited tothese particular combinations. Specific combinations that areparticularly good include, for example, the following blends: from 15%to 30% soybean oil blended with from 70% to 85% cottonseed oil; from 10%to 30% soybean oil blended with from to 50% cottonsed .oil and from 35%'to 50%. winterized cottonseed oil, the preceding blend with up to 50%partially hydrogenated soybean oil (iodine value 105-:

v 110) substituted for an equal amount of cottonseed impurities forsalad oil purposes.

to 50% corn oil (either winterized or unwinterized) sub I stituted foran equal amount of winter oil; any of the preceding blends with up to 25satllower seed oil or sunfiower seed oil substituted for an equal amountof the highest iodine value component; and any of the preceding blendswith up to 15 peanut oil substituted for an equal amount of the lowestiodine value component. All of the aforesaid blends are stated inpercent by weight of the total composition and include therein fromabout 0.005% to about 0.5% crystallization inhibitor. Amounts ofcrystallization inhibitor in excess of about 0.5%, by weight, aregenerally unnecessary as affording no significant added improvemcntinchill test of the blend. These blends have excellent chill tests, showgood flavor stability, and are usable for normal salad oil: purposes.

The components of the oil blends of this invention can include oilsformed by random or directed low temperature interesterification ofanimal and vegetable-fatty materials, followed by removal of highermelting solids formed during the reaction. They can also include othermaterials, such as the acetin fats having one or two short chain acylgroups such as acetyl, which. are dissolved in the oil blends and whichare not deleterious to the normal usage of salad oils.

The following examples will further illustrate the oil blends of thisinvention. The oils used in these examples were subjected to the usualbleaching and deodorizingv treatment in addition to caustic refining toremove undesirablegums and similar materials which occur naturally incrude vegetable oil, but are generally considered These refined 'oilswere not subjected to a Winterizing treatment, however,

unless otherwise specifically mentioned. Table A, below,

indicatesv the approximate fatty acid composition of the oils usedin'the'se examples; and Table B shows other pertinent analytical valuesobtained therefor. All chill test results shown were obtained by theA.O.C.S. method described hereinbefore.

Table A FATTY ACID CONTENT 011 Myristie Palmitic lzalrni- Stearic OleicLinoleic Linolenic Gadolele Erucie Behenic Lignoeeric o ere Cottonseedoil 2 17 54 Peanut oil 3 48 30 4 4 Partially hydrogen oil 12 5 49 32 2Soybean oil 11 5 29 49 6 Safllower oil 8 3 74 Corn oil 13 2 30 55winterized cottonseed oil 1 2 19 57 winterized partially hydrogenatedsoybean oil 11 4 48 35 2 Rapeseed oil 8 2 20 27 6 6 31 Percent by weightdetermined by gas chromatography.

A batch of refined cottonseed oil having a chill test of /3 hour wasdivided into 3 parts. To one part of the oil was added 0.1% by weight ofthe total blend, of acetyl palmitoyl dextrin; to a second part'was added30%, by weight of the total blend, of refined soybean oil; and to thethird part was added the combination of 0.1%, by weight of the totalblend, of acetyl palmitoyl dextrin and 30%, by weight of the totalblend, of refined soy.- bean oil. The chill test. results obtained withthese blends are shown in the following table. All percentages shown inthis example are stated in percent by weight of the total blend.

Table 1 Chill test Oil blend: in hours Cottonseed oil /3 Cottonseedoil+0.1% acetyl palmitoyl dextrin 2%. Cottonseed oil+30% soybean oil /2Cottonseed oil}0.1% acetyl palrnitoyl dextrin and 30% soybean oil 12When dioleoyl hexapalmitoyl sucrose was substituted for the acetylpalmitoyl dextrin in the above example, sub-' stantially similar chilltest results were obtained. The above results show that, althoughneither the crystallization inhibitor nor the soybean oil (winter oil)alone significantly improved the chill test of the cottonseed oil(summer oil), the combination of the inhibitor and soybean oil in thegiven proportions substantially up graded the chill test of cottonseedoil.

EXAMPLE 2 A batch of refined peanut oil having a chill test of hour wasdivided into 7 parts. To each part was added a portion of refined andwinterized cottonseed oil and/or 0.1%, by weight of the total blend, ofan oxygenated and thermally modified hardened vegetable oil hereinreferred to as oxystearin. The said oxystearin was prepared fromhydrogenated cottonseed oil having aniodine'value of about 6 to 8 and abutyro refractive index of about 39:1 at 48 C. The said hydrogenated oilwas bodied with heat at about 225 -250 C. and air blown at the rate ofabout 20 cubic feet per-minute per 1000 pounds of oil until the finalproduct met the following specifications:

Acid number 14.

Iodine value 14. Saponification number 225-240. I-lydroxyl value 30-45.Unsaponifiable matter 0.8%.

Butyro refractive index :1 at 48 C. Molecular weight 925975.

The chill test results obtained with these blends are shown in thefollowing table. All percentages shown in this When refined andpartially hydrogenated soybean oil :WBS substituted for the refinedpeanut oil in the above example, substantially similar chill testresultswere obtained; and when refined safiiower oil was substituted forthe winterized cottonseed oil, substantially similar chill test resultswere again obtained.

. Several blends of the above peanut and winterized cottonseed oils wereprepared. Each blend was trans- -ferred to a separate 250 ml. beaker andheated to 130 C. to remove moisture. The blends were then cooled toabout 80100 C., transferred to Coleman .6-300A cu vettes (25 mm. x 105mm.), corked, and placed in an ice bath which was held at 33.5 F. for aperiod of minutes. The transparency of each blend and a similarlytreated sample of unblended winterized cottonseed oil were photo'-electrically measured with monochromatic light having a wave length of600 m in a Coleman Junior Spectrophotometer. The results showed anincrease in relative transparency, defined as wherein I is thetransmitted intensity of the winterized cottonseed oil and I is thetransmitted intensity. of the V blend, from about 0.5 to about 1.0 whentheconcentraarsena s an accurately reproducible approximation of thepercent inhibitor to either cottonseed oil or partially hydroby weightof winter oil required to be blended with summer oil andcrystallization-inhibitor to provide a substantial improvement in thechill testof the blend.

EXAMPLE 3 A batch of refined cottonseed oil having a chill test of /3hour wasdivided into 5 parts. 'To each part was blended a portion ofrefined corn oil and/or 0.1%, by weight of the total blend, of theoxystearin described in Example 2. The chill test results obtained withthese blends is shown in the following table. All percentages shown inthis example are stated in percent by weight of the total blend.

Table III Chill test Oil blend: in hours I Cottonseed oil /s Cottonseedoil+0.1% oxystearin 2 /2 Cottonseed oil+% corn oi-l /2 Cottonseedoil+30% corn oil /2 Cottonseed oi1+10% corn oil and 0.1% oxystearin I ICottonseed oil+30% corn oil and 0.1% oxystearin When refined saffloweroil, refined and winterized cot-- Several blends of refined rapeseedoil, refined and partially hydrogenated soybean oil, and one or morematerials from the group consisting of refined cottonseed oil, refinedsoybean oil and acetyl palmitoyl dextrin were prepared in theproportions shown in the following table and produced the chill testresults described therein. The amounts of all components of the blendsshown in this example are stated in parts by weight.

Table IV Chill test in hours Oil blend:

Cottonseed oil 100 parts cottonseed ,oil-0i1001 part acetyl palmitoyldextrin 2 /2 Partially hydrogenated soybean oil A 100 parts partiallyhydrogenated soy-beanoil 0,1001 part acetyl palmitoyl dextrin A 10 partsrapeseed oil-70 parts cottonseed oil- 20 parts partially hydrogenatedsoybean oil..- V2 10 parts rapeseed oil-20 parts partially hydrogenatedsoybean oil-70 parts soybean oil 1 /2 10 parts rapeseed oil-70 partscottonseed oil- 20 parts partially hydrogenated soybean oil-- 0.1001part acetyl palmitoyl dextrin 2 10 parts rapeseed oil-20 parts partiallyhydrogenated soybean oil-70 parts soybean oil- 0.1001- part acetylpalmitoyl dextrin 25 The above blend of 10 parts rapeseed oil, 70 partscottonseed oil and 20 parts partially hydrogenated soygenated soybeanoil (summer oils) had negligible effect upon the chill test of thesummer oil. The addition of various amounts of winter oils, such assoybean oil and/or irapeseed oil, tothe summer oils also gave nosignificant It was 1 also found that the blendsof summer and winter oilsimprovement in the chill test of the latter oils.

were substantially improved by the addition of a crystallizationinhibitor only when the summer and winter oil components were blended insuch proportions that the relative transparency (determined according tothe procedure of Example 2) was between 0.5 and 1.0.

EXAMPLE 5 The addition of about 0.1%, by weight of the total blend, ofthe oxystearin described in Example 2 to a blend of 15% peanut oil, 25%winterized cottonseed oil, 25% partially hydrogenated soybean oil and35% safflower oil lengthened the chill test from one hour to about 12hours. Substantial improvements in chill test results are also obtainedby using either 0.005% or 0.5% oxystearin in the above example in placeof 0.1% ,oxystearin.

EXAMPLE 6 The addition of about 0.1%, by weight of the total blend, ofthe oxystearin described in Example'2 to a blend of 15% soybean oil, 35%cottonseed oiland winterized cottonseed oil lengthened the chill testfrom less than 5 /2 hours to greater than 24 hours. The improved blendalso had excellent flavor characteristics.

Each blend in Examples 1-6 which has a chill test in excess of 5 /2hours is suitable for normal salad oil purposes.

The above examples clearly show that substantial improvement in chilltest is obtained when from about 15 to about 85% summer oil .is blendedwith the combination of from about 15 to about 85% winter oil and fromabout 0.005% to about 0.5% crystallization inhibitor, compared to thechill test obtained when'the summer oilis blended with materialindependently selected from the group consisting of said winter oil andsaid crystal-.

be substantially upgraded in chilltest performance by bean oil had arelative transparency of less than 0.1.

relative transparency of about 1.0.

la the above example, the addition of a crystallization the addition offrom about 0.005 to about 0.5% crystallization inhibitor whereas blendswhich do not have such transparency are not significantly improved bysaid crystallization inhibitor.

What is claimed is:

V f 1. A clear liquid glyceride oil composition characterized bysubstantial stability against clouding and stearin deposition whereby ithas a chill test of at least 5 /2 hours at 32 P. which comprises theblend of at least two fatty triglycerideoils at least one of which is asummer oil normally having poor stability against clouding and stearindeposition and at least another of which is a winter oil normally havinggood stability against clouding and stearin deposition with acrystallization inhibitor in an amount of from about 0.005 to about0.5%, by weight of the total composition, the blend containing fromabout 15 to about by weight of the total composition, of summer oil andhaving such proportions of summer oil to winter oil as to satisfy thecondition that the relative transparency, defined as wherein I is thetransmitted intensity of the winter oil component and I is thetransmitted intensity of the uninhibited blend of summer and winteroils, should equal.

9 measured with monochromatic light having a wave length of 600 mg.

2. The composition of claim 1 wherein the crystallization inhibitor isselected from the group consisting of acetyl palmitoyl dextrin, dioleoylhexapalmitoyl sucrose, and oxystearin.

3. The method of substantially improving the chill test of a summer oilnormally having poor stability against clouding and stearin depositionwhich comprises blending it with a winter oil normally having goodstability against clouding and stearin deposition and with acrystallization inhibitor in an amount of from about 0.005% to about0.5%, by weight of the total composition, the blend containing fromabout 15% to about 85% summer oil, by weight of the total composition,and having such proportions of summer oil to winter oil as to satisfythe condition that the relative transparency, defined as wherein I isthe transmitted intensity of the winter oil component and I is thetransmitted intensity of the uninhibited blend of summer and winteroils, should equal about 0.5 to about 1.0 when held at a temperature of33.5 F. for a period of 90 minutes and photoelectrioally measured withmonochromatic light having a Wave length of 600 my.

4. A clear liquid glyceride oil composition characterized by substantialstability against clouding and stearin separation whereby it has a chilltest of at least hours at 32 F. comprising, by weight of thecomposition,

(a) from about to about winter oil selected from the group consisting ofsoybean oil, corn oil, safiiower oil, sunflower seed oil, sesame oil,winterized cottonseed oil, winterized partially hydrogenated soybean oilhaving an I.V. of from about 105 to about 115, and mixtures thereof,

(b) from about 0.005% to about 0.5% crystallization inhibitor and (c)from about 70% to about 85% cottonseed oil.

5. The composition of claim 4 wherein the crystallization inhibitor isselected from the group consisting of acetyl palmitoyl dextrin, dioleoylhexapalmitoyl sucrose, and oxystearin.

6. A clear liquid glyceride oil composition characterized by substantialstability against clouding and stearin separation whereby it has a chilltest of at least 5 /2 hours at 32 F. comprising, by Weight of thecomposition,

(a) from about 25% to about summer oil selected 5 from the groupconsisting of peanut oil, partially hydrogenated soybean oil having anI.V. of from about 105 to about 115, and mixtures thereof,

(b) from about 0.005% to about 0.5 crystallization inhibitor and (c)from about to about winter oil selected from the group consisting ofsoybean oil, corn oil, safflower oil, sunflower seed oil, sesame oil,winterized cottonseed oil, winterized partially hydrogenated soybean oilhaving an I.V. of from about to about 115, and mixtures thereof.

7. The composition of claim 6 wherein the crystallization inhibitor isselected from the group consisting of acetyl palmitoyl dextrin, dioleoylhexapalmitoyl sucrose, and oxystearin.

h. A clear liquid glyceride oil composition having excellent flavor andcharacterized by substantial stability against clouding and stearinseparation whereby it has a chill test of at least 5 /2 hours at 32 F.comprising, by weight of the composition,

(a) from about 10% to about 30% soybean oil,

(b) from about 0.005% to about 0.5 crystallization inhibitor,

(c) from about 35% to about 50% winterized cottonseed oil and (d) fromabout 35% to about 50% cottonseed oil.

9. The composition of claim 8 wherein the crystallization inhibitor isselected from the group consisting of acetyl palmitoyl dextrin, dioleoylhexapalmitoyl sucrose, and oxystearin.

References Cited by the Examiner UNITED STATES PATENTS 40 2,554,872 5/51Musher 99-118 OTHER REFERENCES Bailey: Industrial Oil and Fat Products,1951, Interscience Pub. Inc., N.Y., page 199.

A. LOUIS MONACELL, Primary Examiner.

1. A CLEAR LIQUID GLYCERIDE OIL COMPOSITION CHARACTERIZED BY SUBSTANTIALSTABILITY AGAINST CLOUDING AND STEARIN DEPOSITION WHEREBY IT HAS A CHILLTEST OF AT LEAST 5 1/2 HOURS AT 32*F. WHICH COMPRISES THE BLEND OF A TLEAST TWO FATTY TRIGLYCERIDE OILS AT LEAST ONE OF WHICH IS A SUMMER OILNORMALLY HAVING POOR STABILITY AGAINST CLOUDING AND STEARIN DEPOSITIONAND AT LEAST ANOTHER OF WHICH IS A WINTER OIL NORMALLY HAVING GOODSTABILITY AGAINST CLOUDING AND STEARIN DEPOSTION WITH A CRYSTALLIZATIONINHIBITOR IN AN AMOUNT OF FROM ABOUT 0.005% TO ABOUT 0.5%, BY WEIGHT OFTHE TOTAL COMPOSITION, THE BLEND CONTAINING FROM ABOUT 15% TO ABOUT 85%,BY WEIGHT OF THE TOTAL COMPOSITION, OF SUMMER OIL AND HAVING SUCHPROPORTIONS OF SUMMER OIL TO WINTER OIL AS TO SATISFY THE CONDITION THATTHE RELATIVE TRANSPARENCY, DEFINED AS